Process for the synthesis of plastic materials from unsaturated hydrocarbon oils andsulphur



Patented Dec. 31, 1940 PROCESS FOR THE SYNTHESIS OF PLAs'rIc MATERIALS FROM UNSATURATED HY- DROCARBON OILS AND SULPHUR Herman B. Kipper, Accord, Mass.

No Drawing. Application May 6, 193 Serial No. 206,352

10 Claims.

The novel descriptions, as believed by applicant, contained in the following application, rep resent a continuance of similar work covered by applications Serial Numbers 89,463; 100,818;

111,679; 148,960; 168,394; 179,270, and 187,897.

The specific findings covered more especially in this application pertain to th production of plastic materials produced from olefinic hydrocarbons, such as are given of! as by-products in the cracking of petroleum oils for fabrication of various commercial oils and more especially gasoline.

The reaction chamber used by applicant for carrying out his experimental investigations consists of a chrome-nickel-iron alloy tube about six feet long and one and one-half inches internal diameter and two and three-eighths inches external diameter. Heating 01 the tube was carried out by means of electric resistance furnaces. Two boats," or tubes, made of the same alloy, and slitted lengthwise with a half inch slot for filling, and each about thirty inches long, were used for introduction of the catalytic, or other reaction, materials. into the reaction'chamber be-i fore closing the same with steel plugs, lead gasketed.

As carried out in one of the experiments, into each boat was placed about twenty-five grams of.

sulphur, mixed with three grams ofrfinely divided 80 antimony sulphide. There was then run into the reaction tube about two hundred and fifty grams of olefines, mostly butylenes. These were forced into the tube from another tubular container by' means of nitrogen until some three hundred pounds gauge pressure was registered. .The tube was then closed. and heated 'to about two hundred degrees centigrade during a period or twenty minutes and then gradually raised to a temperature 01 two hundred and fifty degrees over an vators as piperidineand orthotoluidine were added tothe sulphur." They did not appear to aid towards the fo n of a better plastic. Shredded asbestos was also added to the sulphur to render it more "open for reactioning, but the character 01 the finished plastics remained never- 4 theless fairly alike. In other words, a viscous tough product was formed rather than a hard' plastic. This product, applicant found, could be considerably,hardened and a truer plastic produced by treatment with an aldehyde, as formaldehyde, acetaldehyde, croton aldehyde, benzaldehyde and furfural. The latter gave the best 5 product. The viscous product as produced in the reaction chamber was simply thoroughly mixed with the aldehyde and a condensation agent. Barium oxide acted especially advantageously for this purpose. Sodium hydroxide, anhydrous ammom'a, aluminum chloride, sodium sulphide and sodium thiosulphate were also tried and established reaction between the synthesized product and the aldehyde. From five to twenty percent of the latter were used, on basis of synthesized product, and five to fifteen percent of the condensation reagents. Heating 01 the reaction mass was conducted atone hundred to one hundred and fifty degrees centigrade under high pressure.

In my next set-of experiments the rear boat of the reaction tube initially was more or less similarly filled with sulphur, comingled with the various materials such as already noted. The front boat, however, was filled with a mixture of copper and iron oxides carried by shredded asbestos. The basic diflerences in experimentation were due to the use of oxygen with the olefinic gases so as to produce oxidation of the latter. Also oils produced according to my application Serial Number 187,897 from olefinic gases were oxidized concurrently with the reaction used for plastic formation, or they were previously oxidized and then utilized for the reactions in question.

Methods employed for carrying out the latter reaction, that is, those conducted under an oxidizing'atmosphere, were as follows:

Two hundred and fifty grams of olefines, mostly butylenes, were run into a steel cylinder of about forty-five liters capacity and the latter was then filled to two hundred and fifty pounds gauge pressure with a ninety-five percent nitrogen, five percent oxygen mixture. I

The gas mixture, containing the olefines, was then circulated through the reaction tube, heated to two hundred and twenty-five degrees centirade for about an hour at the rate of about one liter per minute. This method proved only semisatisfactory, as the vapor tension of thebutylenes proved to be too low under the operating conditions to give the gas mixture sought] In our next experiment along these lines the olefines were pumped separately through the reaction cham- 'ber and the nitrogen-oxygen mixture was also circulated separately but simultaneously. In a third experiment an oil produced from olefines, according to my application Serial Number 187,897 was pumped through the reaction chamber at the rate-of about two hundred and fifty 5 cubic centimeters per hour and the oxidizing gas was circulated as described in the last experiment. In another experiment the above oil was oxidized with five percent fuming nitric acid after addition of about two percent aluminum chloride to the OH and heating of the same to between fifty and one hundred degrees centigrade. other bydrolyzing metal chlorides, as those of iron, copper, tin and antimony, were also used for this purpose. The oxidation was carried out under powerful it stirring. The oxidized oil was then mixed with about forty percent of sulphur, two percent antimony sulphide, ten percent furfural and three percent barium oxide and heated to one hundred and fifty degrees in a closed tube. By all of these 20 latter four methods, hard plastics were produced.

Some of the yields secured were poor, but it is applicants belief that such poor yields were due rather to experimental difiiculties than to lack of completion of reaction. In the last mentioned an experiment all raw materials utilized were incorporated into the finished plastic.

These oxidized oils, I am now also investigating in paints or drying oils. With a; small percentageof rubber, about one percent, incor- 30 porated with them, very excellent drying oils and of commercial viscosities .are secured.- Rubber is very soluble in the oil. Also polymerizations ,of the oils are being conducted with sodium and other condensation agents. I have secured prod- 35 ucts resembling rubberthrough such application details of al-l'the "runs made would hardly add anything further novel or of value to the art.

50 One of the boats of my reaction tube was filled with twenty-five grams of sulphur, two grams of antimony sulphide, three grams of oxide and twenty-five grams of croton aldehyde and the other boat similarly filled with the exception that the barium oxide was replaced'by solid" cuprous acid phosphate. A few grams of shredded asbestos .was also comingled with the reaction masses of sulphur, etc. The reaction tube was closed and two hundred and fifty grams of olefines, mostly butylenes, were forced into the tube by nitrogen gas until the reaction tube registered three hundred pounds gauge pressure. The tube was then raised rapidly to two hundred degrees and maintained at the latter temperature for three hours. The reaction tube was opened subsequently. to cooling. Hard, excellent plastics were secured. About two hundred and fifty grams of plastic material were obtained. A plastic made 70 according to. the above method in which heating, after the reaction temperature had been reached, was continued for only an hour, was tough and viscous in character. Thus it will be noted that hardness" securable in the finished plastic is 75 dependent upon the period of heating or of reaction and that this specific quality is enhanced as the said period is lengthened.

With furfura-l I used only a hundred and fifty degree reaction temperature. The same temperature was employed when using benzaldehyde and 5 salicylaldehyde.

In my final work the oils, treated with hydrolyzlng metal chlorides, as aluminum chloride, cupric chloride, antimony chloride or ferric'chloride andnitrlcacid, were further polymerized by 2.1- 10 lowing to stand for several weeks at room temperatures, or heated to a temperature of fifty to sixty degrees centigrade, in the presence of a small percentage of aluminum chloride. The oils were thereby further polymerized to give viscous elastic-like masses. Treatment with sulphur, or sulphur and antimony chloride, was then conducted at one hundred and fifty to two hundred degrees centigrade in my reaction tube, either at atmospheric pressure or under superatmospheric pressures exerted by an inert gas, as nitrogen. From twenty-five to fifty percent of sulphur was used and small percentages of antimony sulphide. With ten to fifteen percent of sulphur, tough, elastic materials resembling vulcanized rubber were secured. Small percentages of'socalled rubber accelerators were likewise employed, especially those used with syntheticrubbers, as piperidine, thiourea and orthotoluidine. Also to destroy any aluminum chloride that might re- 0 main in the tough viscous mass used for plastic formation, a small percentage of sodium sulphide was incorporated with and thoroughly worked into the said mass. Also aldehydes were used in the reaction, ten to twenty percent. Croton aldehyde and furfural hardened the plastics formed,

but in all cases where over thirty percent of sulphur was used relatively hard, excellent plastics were produced. Rubber, up to ten percent, was also added to the oils or viscous masses before 40 plastic formation. As has been noted, rubber is very soluble in the oils and the quality of the plastic formed through its incorporation appeared possibly better. i

I also experimented with adding urea, thiourea and phenol to the sulphur mass. The aldehydes were then used in excess proportions to those required for plastic formation from the chemicals justmentioned. Thus, plastics well known to the art were produced simultaneously and as a part of, or comingled with, my novel plastic materials. In this manner, plastics having a very wide range of properties can be fabricated.

As to be probably expected, .the viscous elasticlike masses produced by treatment of the condensed oleflnes with aluminum chloride and nitric acid, when reacted with sulphurchlorides, either the monoor di-chloride. give first tough pliable elastic bodies and as the percentage of the sulphurchloride is increased, hard plastic materials are formed. The percentage of the sulphurchloride used was made as high as one hundred percent before the plastic showed any noticeable decomposition, that is, with the formation of free carbon.

These plastics show thermoplastic qualities, softening between one hundred and fifty and two hundred degrees centigrade, at which temperatures they can be-readily pressurelmolded.

Applicant believes that the examples cited illustrate basically his novel processing for plastic fabrications. Combinations of raw material specifications, operating conditions could, of course, be multiplied ad infinitum without actually digressing from his basically novel findings.

I claim: 1 I 1. In a process for the production of plastic materials .he step of reacting olefines, organic aldehydes and sulphur at superatmospheric pressures and temperatures.

2. In a process for the production of plastic materials the step of reacting olefines, organic aldehydes, sulphur and antimony sulphide at superatmospheric pressures and temperatures.

3. In a process for the production of plastic materials the step of reacting oleflnes, organic aldehydes, sulphu. and antimony sulphide at superatmospheric temperatures and pressures.

the latter partially maintained by means of an inert gas.

4. In a process for the production of plastic materials the step of reacting olefines, sulphur and unsaturated hydrocarbon oils, previously treated with hydrolyzing metal chlorides and nitric acid, at supera'tmospheric temperatures and pressures.

5. In a process for the production of plastic materials the step of reacting olefines, sulphur, aldehydes and unsaturated hydrocarbon oils, previously treated with hydrolyzing metal chlorides and nitric acid, at superatmospheric temperatures and pressures.

6. In a process for the production of plastic to oils and treated with hydrolyzing metal chlorides and nitric acid subsequently to condensation, with sulphur at superatmospheric temperatures.

8. In a process for the production of plastic materials the step of reacting olefines, condensed at superatmospheric pressures and temperatures tooils and treated with hydrolyzing metal chlorides and nitric acid subsequently to condensation, with sulphur at atmospheric temperatures and pressures, the latter partially maintained -b means of an inertgas.

9. In a process for the production of plastic materials the step of reacting olefines, condensed at superatmospheric pressures and temperatures to oils and treated with hydrolyzing metal chlorides and nitric acid subsequently to condensation, with sulphur, antimony sulphide, litharge, piperidine and thiourea at superatmospheric temperatures and pressures, the latter partially maintained by means of an inert gas.

10. In a process for the production of plastic materials the step of reacting butylenes, condensed at superatmospheric pressures and temperatures to oils and treated with aluminum chloride and nitric acid subsequently to condensation, with sulphur, antimony sulphide, litharge, piperidine and thiourea at two hundred degrees centigrade and two hundred pounds pressure,

said pressure maintained by means of nitrogen.

HERMAN B. KIPPER. 

